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Title: Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation

We report the room temperature synthesis and structural characterization of a μ2-hydroxobridged PuIV dimer obtained from an acidic, nitric acid solution. The discrete Pu2(OH)2(NO3)6(H2O)4 moiety crystallized with two distinct crystal structures, (1) [Pu2(OH)2(NO3)6(H2O)4]2·11H2O and (2) Pu2(OH)2(NO3)6(H2O)4·2H2O, which differ primarily in the number of incorporated water molecules. High-energy X-ray scattering (HEXS) data obtained from the mother liquor showed evidence of a correlation at 3.7(10) Å but only after concentration of the stock solution. This distance is consistent with the dihydroxo-bridged distance of 3.799(1) Å seen in the solid-state structure as well as with the known Pu-Pu distance in PuO2. The structural characterization of a dihydroxo-bridged Pu moiety is discussed in terms of its relevance to the underlying mechanisms of tetravalent-metal-ion condensation
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Publication Date:
OSTI Identifier:
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 54; Journal Issue: 21
American Chemical Society (ACS)
Research Org:
Argonne National Laboratory (ANL)
Sponsoring Org:
USDOE Office of Science - Office of Basic Energy Sciences
Country of Publication:
United States
Actinide; hydrolysis; hydroxo-bridged dimers; metal-oxide clusters; plutonium